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Guanine binding to gold nanoparticles through nonbonding interactions.

Xi Zhang1, Chang Q Sun, Hajime Hirao

  • 1Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore637371. hirao@ntu.edu.sg.

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Summary

Gold nanoparticles bind DNA bases through charge transfer and orbital interactions. Smaller nanoparticles exhibit stronger binding due to increased surface effects, crucial for gene delivery applications.

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Area of Science:

  • Computational Chemistry
  • Materials Science
  • Nanotechnology
  • Biophysics

Background:

  • Gold nanoparticles (AuNPs) are promising nanocarriers for gene delivery.
  • The precise binding mechanism between AuNPs and DNA bases is not fully understood.
  • Guanine is a key DNA base with implications for nanoparticle interactions.

Purpose of the Study:

  • To elucidate the binding mechanism between gold nanoparticles and guanine.
  • To investigate the role of nanoparticle size and surface effects on binding.
  • To explore the electronic interactions governing AuNP-guanine complex formation.

Main Methods:

  • Density functional theory (DFT) calculations were employed.
  • Calculations were performed on cuboctahedral gold nanoparticles (Au(N), N = 13, 55, 147).
  • Dispersion corrections and fragment orbital analysis were utilized to study electronic structure and bonding.

Main Results:

  • Negative charge transfer from the nanoparticle interior to the surface was observed due to the surface quantum trapping effect.
  • Valence states shifted towards the Fermi level, enhancing participation in guanine binding.
  • Electron donation from guanine's nitrogen lone-pair orbital to the gold cluster occurred, alongside potential π back-donation and hydrogen bonding.

Conclusions:

  • The binding mechanism involves charge transfer and orbital interactions, influenced by nanoparticle size.
  • Smaller gold nanoparticles exhibit more pronounced surface effects, leading to stronger guanine binding.
  • Understanding these interactions is vital for optimizing gold nanoparticles in gene delivery systems.